Decorative sheet and decorative material

ABSTRACT

The use of a pearl pigment as a decorative material for the interior of automobile parts is known to weaken the weather resistance of these parts. Improved weather resistance is achieved by providing a decorative sheet  10 , wherein a pearl ink layer  2  comprising a pearl pigment is provided on a base material sheet  1 , and the pearl ink layer comprises: at least a vinyl chloride-vinyl acetate copolymer as a binder resin; and the pearl pigment obtained by coating mica with a titanium dioxide, and further, coating the surface thereof with a metal oxide and/or a metal oxide hydrate of metals other than a titanium such as a zirconium, a silicon and the like. The titanium dioxide is preferably of a rutile type. Moreover, the base material sheet is preferably a resin sheet of an acrylic resin. A decorative material  20  can be obtained by laminating the above mentioned decorative sheet on a surface of a base material  5 , which is a resin molded body.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a decorative sheet having pearl-likebrilliance, and a decorative material having this decorative sheetlaminated on a base material such as a resin molded body and the like.Particularly, the present invention relates to a decorative sheet anddecorative material having excellent weather resistance, suitable foruses requiring high weather resistance performance such as automobileinteriors and other uses.

2. Description of the Related Art

Decorative sheets are used in various uses such as construction interiorand exterior materials, construction materials, furniture, or automobileinterior and exterior materials and the like. Decorative sheets areoften required to have weather resistance, paint feeling and the like.In such cases, an acrylic resin sheet excellent in transparency is usedas a base material sheet on the front surface side. For example, as adecorative sheet capable of being molded and laminated on the surface ofa resin molded item and the like, a decorative sheet and the like havingconfiguration of the following layers laminated in this order (see,Japanese Patent Application Laid-Open (JP-A) No. 2001-232660) can belisted: on the surface side, a transparent acrylic resin sheet; an inklayer having a design expressed using a mixture, of an acrylic resin anda vinyl chloride-vinyl acetate copolymer, as a binder resin; an adhesivelayer using a mixture of an acrylic resin and a vinyl chloride-vinylacetate copolymer as a binder resin; and as a resin sheet on the backside, a resin sheet having a coloring masking property of an ABS resin(acrylonitrile-butadiene-styrene copolymer).

To express a design of a decorative sheet, brilliance such as metalgloss feeling, pearl gloss feeling and the like, are required in somecases. For imparting such brilliance to a decorative sheet, a metalvacuum evaporation layer is provided in some cases. However, brilliantpigments such as a metal powder, pearl pigment and the like are oftencontained in an ink layer, resin sheet and the like is contained in theink layer, the resin sheet or the like (see, JP-A No. 2002-210907) inmany cases. As the brilliant pigment to be used, a powder of a metalsuch as aluminum and the like is used when a metal gloss feeling isexpressed as a brilliance property, a pearl pigment such as titaniumdioxide coated mica and the like is use when a pearl gloss feeling isexpressed, in general.

Though a pearl gloss feeling gives a luxurious feeling as compared witha metal gloss feeling, when titanium dioxide coated mica which is ageneral pearl pigment is used, there occurs a problem of deteriorationof the weather resistance. When the weather resistance is deteriorated,there will be a failure that a decorative sheet or decorative materialis peeled off at a pearl ink layer containing an added pearl pigment.When the weather resistance is deficient, measures are usually takenthat a resin excellent in the weather resistance such as an acrylicresin and the like is used as the resin of a base material sheet, or anultraviolet absorber or a light stabilizer such as a binderedamine-based radical scavenger and the like is added in the resin of abase material sheet. However, these countermeasures are limited sincethe light stabilizer tends to bleed out from the surface to causewhitening and the like.

For evaluation of the weather resistance, an artificial acceleratedexposure test imitating an atmospheric exposure test at laboratory levelis common, since a result of good reproducibility is obtained in ashorter period of time. And as its test light source, a sunshine carbonarc lamp is often used for a long time. However, a xenon arc lamp givesa result closer to weather resistance under natural environments thanthe sunshine carbon arc lamp. Therefore, particularly currently, a testby a xenon arc lamp tends to be adopted when weather resistance isevaluated more precisely. For example, there may be a case, though theweather resistance performance evaluated by the sunshine carbon arc lampis excellent, the weather resistance performance is poor when evaluatedby the xenon arc lamp.

SUMMARY OF THE INVENTION

An object of the present invention is to obtain a good weatherresistance in a decorative sheet using a pearl pigment even if it isevaluated by a xenon arc lamp. Moreover, another object of the presentinvention is to provide a decorative material obtained by laminatingsuch a decorative sheet on a base material such as a resin molded itemand the like, for example, a decorative material for vehicles such asautomobile interior parts and the like.

For solving the above mentioned problems, a decorative material of thepresent invention has a configuration that, a pearl ink layer comprisinga pearl pigment is provided on a base material sheet, and the pearl inklayer comprises: at least a vinyl chloride-vinyl acetate copolymer as abinder resin; and the pearl pigment obtained by coating mica with atitanium dioxide, and further, coating the surface thereof with a metaloxide and/or a metal oxide hydrate of metals other than a titanium suchas a zirconium, a silicon and the like.

In the titanium dioxide coated mica conventionally used as a pearlpigment promotes a photodecomposition of a binder resin, because thetitanium dioxide on its outermost surface acts as a photocatalyst.However, by having the above mentioned configuration, even though thesheet has a pearl gloss feeling, the weather resistance can be improvedby coating the surface of the titanium dioxide with other substance inorder to inhibit the action. Further, even when evaluated by a xenon arclamp, the weather resistance can be improved.

Moreover, the decorative sheet of the present invention has aconfiguration in which the titanium dioxide is of a rutile type in theabove mentioned configuration.

By such a configuration, the photocatalyst action of the titaniumdioxide itself can be decreased as compared with anatase type, andresultantly, the weather resistance can be further improved.

In either of the above mentioned configuration, the decorative sheet ofthe present invention further has a configuration in which, the metal ofthe metal oxide and/or metal oxide hydrate is the zirconium.

By having such configuration, the weather resistance can be securelyimproved.

In any of the above mentioned configuration, the decorative sheet of thepresent invention further has a configuration in which, the basematerial sheet is a resin sheet of an acrylic resin.

By having such configuration, the weather resistance is improved alsofrom the standpoint of a resin used for the material of the basematerial sheet.

Moreover, the decorative material of the present invention has aconfiguration in which any one of the above mentioned decorative sheetis laminated on the surface of a resin molded body.

This configuration is one preferable application example of the abovementioned decorative sheet, and by adopting such a configuration, theeffect of the above mentioned decorative sheet can be imparted to itemshaving shape other than sheet such as a plate, a three dimensional bodyand the like, so that the weather resistance of the decorative materialhaving a pearl gloss feeling can be improved even in the case ofevaluating by a xenon arc lamp and the like.

In the above mentioned configuration of the decorative material, thedecorative material of the present invention further has a configurationin which, the resin of the resin molded body is made of an ABS resin,polycarbonate resin or of both these resins, and

the base material sheet of the decorative sheet is a resin sheet of anacrylic resin.

This configuration is one preferable embodiment of the above mentioneddecorative material, as the decorative material using the resin which isrelatively common as a resin of a resin molded body, can impart a pearlgloss feeling together with the weather resistance.

One preferable embodiment of the decorative material of the presentinvention is any one of the above mentioned decorative materials, andused as a decorative material for vehicles.

This configuration shows preferable applications of any one of the abovementioned decorative materials, and shows, for example, that a pearlgloss feeling can be imparted together with the weather resistance, as adecorative material for automobile interiors.

(1) According to the decorative sheet of the present invention, even ifmica coated with titanium dioxide is used as a pearl pigment, (since itssurface is further coated with a metal oxide and/or metal oxide hydrateof metals other than titanium) photodecomposition of a binder resin bythe photocatalysis action of titanium dioxide is inhibited, and weatherresistance can be improved even if a pearl gloss feeling is imparted.Also, when evaluated by a xenon arc lamp, the weather resistance can beimproved.

(2) Further, when titanium dioxide is of a rutile type, the weatherresistance can be further improved as compared with that of an anatasetype.

(3) When the metal of the above mentioned metal oxide and/or metal oxidehydrate is a zirconium, the weather resistance can be securely improved.

(4) When the base material sheet is a resin sheet of an acrylic resin,the weather resistance is improved also from the standpoint of the resinmaterial of a resin material sheet.

(5) According to the decorative material of the present invention, eacheffect of the above mentioned decorative sheet can be obtained, and theweather resistance can be improved even if a pearl gloss feeling isimparted, and a decorative material obtained by laminating a decorativesheet on a resin molded body, of an ABS resin, polycarbonate resin andthe like, can be made suitable for automobile uses. Further, also whenevaluated by a xenon arc lamp, the weather resistance can be improved.

BRIEF DESCRIPTION OF THE DRAWING

FIGS. 1A to 1D are sectional views showing embodiments of the decorativesheets and decorative material according to the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Embodiments of the present invention will be explained below.

[Summary]

First, FIGS. 1A to 1C are sectional views showing some embodiments ofdecorative sheet of the present invention and a decorative materialobtained by laminating the decorative sheet on a base material such as aresin molded body and the like.

FIG. 1A shows a basic configuration example of a decorative sheet 10, inwhich on one surface of a base material sheet 1 made of a transparentacrylic resin sheet and the like, a pearl ink layer 2, comprising apearl pigment peculiar to the present invention, is formed. This pearlpigment is a pearl pigment obtained by coating mica with a titaniumdioxide, and further, coating the surface thereof with a metal oxideand/or metal oxide hydrate of metals other than a titanium such as azirconium, a silicon and the like. It should be understood that, a pearlink layer may be solid on the whole surface or formed in a pattern of adesign.

A decorative sheet 10 shown in FIG. 1B is a configuration example inwhich an adhesive layer 3 is further formed on (lower part of thedrawing) the pearl ink layer 2, in the configuration of FIG. 1A.Moreover, a decorative sheet 10 shown in FIG. 1C is a configurationexample in which design layers 4, formed of an ink comprising no pearlpigment, are provided in between the base material sheet 1 and the pearlink layer 2. FIG. 1D is a sectional view showing one embodiment of adecorative material 20 obtained by laminating the decorative sheet 10,for example as shown in FIGS. 1A to 1C, on a base material 5 such as aresin molded body and the like made of an ABS resin and the like.

[Pearl Ink Layer]

The pearl ink layer 2 is an ink layer containing a pearl pigment. As thepearl pigment, in the present invention, a mica based pearl pigment isused, which is obtained by not only coating the surface of mica withtitanium dioxide like conventional titanium dioxide coated mica, butfurther coating its surface with a metal oxide and/or metal oxidehydrate of metals other than titanium such as zirconium, silicon,aluminum, cerium and the like. The coating amount of a metal oxideand/or metal oxide hydrate is about 4 to 20 wt % based on the totalweight of the pearl pigment. By this, photodecomposition anddeterioration of a binder resin of the pearl ink layer, due to thephotocatalysis action of titanium dioxide on the surface, which arisesin the conventional titanium dioxide coated mica can be inhibited. As aresult, substantial solutions can be provided to the cause of thedecrease in the weather resistance.

In order to coat the surface, after being coated with the titaniumdioxide, further with the metal oxide or metal oxide hydrate of a metalsuch as zirconium, silicon and the like, or with both the metal oxideand the metal oxide hydrate thereof, a known method, for example, inwhich these are deposited on the surface from the corresponding metalsalt liquid, may be adopted. In the case of zirconium, the metal oxidehydrate is a zirconium dioxide hydrate. And this is also calledzirconium hydroxide.

As the titanium dioxide to be coated on the surface of mica, that of arutile type is more preferable than that of an anatase type. The reasonfor this is that the photocatalysis action of the rutile type is smallerthan the anatase type (anatase type: 3.2 eV, rutile type: 3.0 eV)because the band gap is small. As a result, the promoting action ofphoto-deterioration of the binder resin is smaller, and weatherresistance will be improved.

To improve physical properties such as dispersion stability and thelike, the surface of the above mentioned specific pearl pigment mayfurther be coated with an organic coupling agent. As the organiccoupling agent, for example, a silane coupling agent is used. As thesilane coupling agent, conventionally known agents may be appropriatelyselected and used depending on the applications and the like.

The particle size of the pearl pigment may be determined appropriatelydepending on the required pearl design, transparency and the like. Forexample, it is about 5 to 25 μm. The shape of the pearl pigment has thesame scale-like shaped foil same as that of usual pearl pigments.

The content of the pearl pigment may also be appropriately determineddepending on the required pearl design and the like. For example, it isabout 5 to 60 wt % based on the resin component.

The thickness of the pearl ink layer, containing the specific pearlpigment as described above, may be an appropriate thickness depending onthe required pearl design and the like. For example, it is about 1 to 10μm.

The layer positional relationship of the pearl ink layer and the basematerial sheet is not particularly limited in basic. For example, anyone of the front surface, rear surface, front and rear surfaces, andinner surface (in the case of multilayered base material sheet) of thebase material sheet may be adopted. However, from the standpoint of theweather resistance, it is more preferable that the base material sheetis on the observation side (sunlight side) since the pearl ink layer canbe protected from light by the base material sheet, and in this respect,rear surface or inner surface of the base material sheet is morepreferable than the front surface.

As the binder resin of the pearl ink layer, appropriate resins such, asurethane resins, polyester resins, acrylic resins and the like, may beused in basic depending on the layer material such as the material resinof the base material sheet and the like. However, in the presentinvention, at least a vinyl chloride-vinyl acetate copolymer is used.Though the vinyl chloride-vinyl acetate copolymer may be used as abinder resin by itself, in view of adhesion and the like, it ispreferable that the copolymer is used together with other resins, forexample, to be used as a mixed resin with an acrylic resin and the like.The vinyl chloride-vinyl acetate copolymer is particularly used in thepresent invention because of the good adhesion with various resins suchas, for example, an acrylic resin and the like.

The vinyl chloride-vinyl acetate copolymer is a binder resin that theeffect of improving the weather resistance of the specific pearl pigmentis easily manifested remarkably in a weather resistance test by a xenonarc lamp. The reason for this is that light with wavelength of 364 nmhas a tendency to deteriorate the vinyl chloride-vinyl acetatecopolymer, and the xenon arc lamp contains components of the wavelengthin larger amount than a sunshine carbon arc lamp. In this respect, anacrylic resin contains no such weak light components and need not to beconcerned, while the vinyl chloride-vinyl acetate copolymer hasconsiderable physical properties from the standpoint of adhesion and thelike. Even if this vinyl chloride-vinyl acetate copolymer is used, sucha remarkable function and effect, that the weather resistance in theweather resistance test by the xenon arc lamp can be improved, can beobtained in the present invention.

Formation of the pearl ink layer may be conducted by known formingmethods such as a printing method, coating method and the like, and inthe case of forming a solid layer on the entire surface, either of theabove method can be used. Though the pearl ink layer 2 shown in theexamples of the decorative sheet in FIGS. 1A to 1C are drawn as solidlayers on the entire surface, these are concept diagrams forexplanation, and layers in the form of a pattern are also included.

For adjusting its physical properties, various additives such ascoloring agents, fillers, ultraviolet absorbers, and light stabilizerssuch as a hindered amine-based radical scavenger and the like areappropriately added to the pearl ink layer as necessity.

[Base Material Sheet]

The base material sheet 1 is not particularly limited basically, and aresin sheet, paper, metal foil and the like corresponding to the usesmay be appropriately used. However, when the base material sheet isplaced on the observation side of the pearl ink layer, transparency isrequired. When the decorative sheet is drawn by vacuum molding,discharge mold decorating and the like, moldability is also necessary.Typical examples of such a base material sheet include resin sheets madeof thermoplastic resins.

Examples of the thermoplastic resin used for the resins sheet includepolyolefin-based resins such as polyethylene, polypropylene,polymethylpentene, polybutene, ionomer, ethylene-propylene copolymer,ethylene-propylene-butene copolymer, olefin-based thermoplasticelastomer and the like, polyester resins such as polybutyleneterephthalate, polyester-based thermoplastic elastomers, completeamorphous polyester and the like, acrylic resins such aspolymethyl(meth)acrylate, polybutyl(meth)acrylate,methyl(meth)acrylate-butyl(meth)acrylate copolymer, styrene-methyl(meth)acrylate copolymer and the like [(meth)acrylic means acrylic ormethacrylic], polycarbonate resins, polystyrene resins, vinyl chlorideresins and the like.

Among the above, an acrylic resin is one of the preferable resins due toexcellent transparency and weather resistance. The reason for this isthat design rich in luxurious feeling such as surface gloss and thelike, or painting feeling can be imparted by the excellent transparencyof the acrylic resins. Moreover, the acrylic resins also have a meritthat surface physical properties such as the weather resistance andscratch resistance and the like are also improved as compared with acase of using a polyolefin-based resin or the like.

For adjusting its physical properties, various additives such aslubricants, friction reducing agents, fillers, coloring agents,ultraviolet absorbers, and light stabilizers such as a hinderedamine-based radical scavenger and the like are appropriately added tothe resin sheet as necessity.

In the case of the resin sheet, the thickness may be appropriatelyadjusted depending on cost, moldability, design (painting feeling) andthe like, and it is usually about 30 to 200 μm.

[Adhesive Layer]

An adhesive layer 3 is appropriately provided, if necessary, on thesurface of an adhesive body side, for increasing adhesive force inadhering and laminating the decorative sheet on the adhesive body suchas the base material and the like [see, FIG. 1B]. As the adhesive layer,known adhesives maybe used depending on the uses, and for example,thermoplastic resins such as a vinyl acetate resin, vinyl chloride-vinylacetate copolymer, thermoplastic polyester resin, polyamide resin,ionomer, chlorinated polyolefin resin, thermoplastic urethane resin andthe like, thermo-setting resins such as phenol resins, epoxy resins andthe like, or rubber-based resins and the like are used. The adhesivelayer can be formed by known printing or coating methods. The thicknessof the adhesive layer is not particularly limited. For example, it isabout 5 to 20 μm.

[Design Layer]

A design layer 4 is the ink layer containing no pearl pigment and onwhich a design is expressed. The design may be a woody pattern or thelike, or the entire surface may be of a solid pattern. Though the designlayer is appropriately provided as necessity, it is usually provided forimproving the design. Also, the design layer may be formed by knownprinting or coating methods (in the case of the entire surface is of asolid pattern) like the pearl ink layer. The binder resin of the designlayer is the same as that of the pearl ink layer so that furtherexplanations are omitted. The design layer usually contains a coloringagent, and may also contain brilliant pigments other than the pearlpigment, that is, metal pigments such as a metal powder and the like. Asthe coloring agent, known coloring agents may be appropriately used.

[Base Material]

When the decorative sheet as described above is laminated, appropriatelyusing an adhesive, on the base material of resin, wood and the like, thedecorative material 20 as shown in FIG. 1D is obtained. The basematerial 5 is not particularly limited, and conventionally known variousbase materials are used depending on the uses. A method of laminatingthe decorative sheet and the base material is also not particularlylimited, and conventionally known various laminating methods may beappropriately adopted. For example, in a discharge mold decoratingmethod, the decorative sheet can be molded and laminated on a surface ofa three dimensional resin molded body. Regarding molding of thedecorative sheet, a discharge molding mold and a vacuum molding mold canbe used together, or a sheet can be molded in a vacuum molding-dedicatedmold, and then, the molded decorative sheet can be installed in thedischarge molding mold and be discharge molded. The latter is one kindof an insert molding.

The resin of the resin molded body is not particularly limited, andconventionally known resins depending on the uses are appropriatelyselected and used. For example, for vehicle uses such as automobileinteriors and the like, an ABS resin, polycarbonate resin,ABS/polycarbonate mixed resin are typically used, and additionally,polypropylene resins and the like are also used.

[Uses of Decorative Sheet and Decorative Material]

The uses of the decorative sheet and decorative material of the presentinvention are not particularly limited, and the uses requiring theweather resistance are particularly preferable since the property can beutilized. Needless to say, the present invention can be preferably beused in the uses in which a pearl gloss feeling is required as design.Specifically, automobile uses such as automobile interiors such as adashboard panel, door panel, lower panel and the like, automobileexteriors such as a car body, mole and the like are suitable examples.Mentioning examples other than automobile uses, construction uses suchas a window frame (sash), door frame, door, wall plate, floor plate,wainscot panel, veranda, roof surface material, shelf, gate, gatepillar, door guard and the like, and furniture uses such as a desk,chest of drawers and the like.

EXAMPLES

The present invention will be further explained in detail by thefollowing examples and comparative examples.

Example 1

The decorative sheet 10 having a configuration as shown in FIG. 1B wasproduced as described below.

First, a transparent colorless resin sheet having a thickness of 125 μmmade PMMA (polymethyl methacrylate) was prepared as the base materialsheet 1. On the surface to be used as a rear side of this base materialsheet, the below mentioned ink was gravure-printed so as to form thepearl ink layer 2 of 2 μm when dried (also in the following procedures)with the entire surface being of a solid pattern. The ink used for theabove pearl ink layer comprises: based on 15 parts by weight of a binderresin, of a mixed resin containing a vinyl chloride-vinyl acetatecopolymer and an acrylic resin at a weight ratio of 1:1; 15 parts byweight of a pearl pigment, obtained by coating the surface of mica withrutile type titanium dioxide, zirconium dioxide and silane couplingagent in this order; 3 parts by weight of a dispersion stabilizer andplasticizer in total; and 67 parts by weight of a solvent. Subsequently,an adhesive layer 3 of the vinyl chloride-vinyl acetate copolymer havinga thickness of 2 μm was also formed by gravure printing on the pearl inklayer, thus producing a desired decorative sheet 10 as shown in FIG. 1B.

Further, this decorative sheet 10 was laminated on the base materialsheet 5, which is a resin molded body made of an ABS resin, by softeningby vacuum molding by heating with a radiation heating type heating panelat 340° C. on an discharge molding mold (female mold) acting also as avacuum molding mold, then, an ABS resin was discharge molded underconditions of a mold temperature of 50° C. and an discharge temperatureof 235° C. Thus, a desired decorative material 20, as shown in FIG. 1D,was produced.

Example 2

A desired decorative material 20 as shown in FIG. 1D was produced, bylaminating on the base material 5 of a resin molded body, in the samemanner as in Example 1 except that, in producing a decorative materialusing the decorative sheet produced in Example 1, vacuum molding of thedecorative sheet was conducted in a dedicated vacuum molding mold, then,an ABS resin was filled into an discharge molding mold and was dischargemolded.

Comparative Example 1

A decorative sheet and a decorative material were produced in the samemanner as in Example 1 except that a pigment, obtained by only coatingthe surface of mica with rutile type titanium dioxide, was used as thepearl pigment used in the pearl ink layer in Example 1.

Comparative Example 2

A decorative sheet and a decorative material were produced in the samemanner as in Example 1 except that a pigment, obtained by only coatingthe surface of mica with anatase type titanium dioxide, was used as thepearl pigment used in the pearl ink layer, in Example 1.

Comparative Example 3

A decorative material was produced in the same manner as in Example 2except that a decorative material was produced using the decorativesheet in Comparative Example 1 instead of the decorative sheet inExample 1, in Example 2.

Comparative Example 4

A decorative material was produced in the same manner as in Example 2except that a decorative material was produced using the decorativesheet in Comparative Example 2 instead of the decorative sheet inExample 1, in Example 2.

[Performance Evaluation]

The weather resistance of the decorative materials produced in theexamples and comparative examples was evaluated by an artificialaccelerated exposure test using a xenon arc lamp. The testing conditionswere: a black panel temperature of 89° C.; a humidity of 50 RH %;continuous irradiation (only irradiation with light, no rain): and anirradiating time of 500 hours. After the test, (cross cut) adhesion wasevaluated by a cross cut tape method, and an adhesive cellophane tapewas stuck on 100 (10 longitudinal×10 lateral) squares formed with autility knife, then, peeled off quickly. When the number of squaresremaining without peeling off with the tape was 100 (100/100), it wasevaluation as “good”, and when at least one square was peeled off(99/100 or less), it was evaluation as “no good”.

As a result, in both of the examples, adhesion was good, and the weatherresistance evaluated by the xenon arc lamp test was good, as shown inTable 1. However, in all of the comparative examples, adhesion was nogood, and sufficient weather resistance could not be obtained.

TABLE 1 RESULTS OF PERFORMANCE EVALUATION Cross cut adhesion Weatherresistance Example 1 100/100  Good Example 2 100/100  Good ComparativeExample 1 38/100 No good Comparative Example 2 11/100 No good (verypoor) Comparative Example 3 38/100 No good Comparative Example 4 11/100No good (very poor)

1. A decorative sheet, wherein a pearl ink layer comprising a pearlpigment is provided on a base material sheet, and the pearl ink layercomprises: at least a vinyl chloride-vinyl acetate copolymer as a binderresin; and a pearl pigment obtained by coating mica with a layercontaining titanium dioxide, and further, coating the surface thereofwith a metal oxide and/or a metal oxide hydrate of metals other thantitanium, and wherein an adhesive layer comprising a vinylchloride-vinyl acetate copolymer is formed on the pearl ink layer so asto be provided as an outermost layer.
 2. The decorative sheet accordingto claim 1, wherein the metal of the metal oxide and/or metal oxidehydrate is zirconium.
 3. The decorative sheet according to claim 1,wherein the base material sheet is a resin sheet of an acrylic resin. 4.The decorative material comprising the decorative sheet according toclaim 1 laminated on the surface of a resin molded body.
 5. Thedecorative material according to claim 4, wherein the resin of the resinmolded body is made of an ABS resin, polycarbonate resin or of boththese resins, and the base material sheet of the decorative sheet is aresin sheet of an acrylic resin.
 6. The decorative material according toclaim 5, wherein the decorative material is used for vehicles.
 7. Thedecorative material according to claim 4, wherein the decorativematerial is used for vehicles.
 8. The decorative sheet according toclaim 1, wherein the pearl pigment is further coated with a silanecoupling agent.
 9. The decorative sheet according to claim 8, wherein acoating amount of the metal oxide and/or metal oxide hydrate is 4 to 20wt % based on a total weight of the pearl pigment.
 10. The decorativesheet according to claim 1, wherein a coating amount of the metal oxideand/or metal oxide hydrate is 4 to 20 wt % based on a total weight ofthe pearl pigment.